6533b830fe1ef96bd1296744
RESEARCH PRODUCT
Reactivity of Nickel(II) Porphyrins in oCVD Processes—Polymerisation, Intramolecular Cyclisation and Chlorination
Gilles FracheKamal BabaNicolas D. BoscherKatja HeinzeOliver BackGiuseppe Bengasisubject
Conjugated systemporphyrins010402 general chemistryPhotochemistry01 natural sciencesCatalysischemical vapor depositionnickelchemistry.chemical_compoundReactivity (chemistry)Full Paper010405 organic chemistryOrganic ChemistryRegioselectivityGeneral ChemistryFull PapersPorphyrin0104 chemical sciencesMonomerthin filmschemistryPolymerizationpolymerizationChemical Vapor Deposition | Hot PaperOxidative coupling of methaneCyclic voltammetrydescription
Abstract Oxidative chemical vapour deposition of (5,15‐diphenylporphyrinato)nickel(II) (NiDPP) with iron(III) chloride as oxidant yielded a conjugated poly(metalloporphyrin) as a highly coloured thin film, which is potentially useful for optoelectronic applications. This study clarified the reactive sites of the porphyrin monomer NiDPP by HRMS, UV/Vis/NIR spectroscopy, cyclic voltammetry and EPR spectroscopy in combination with quantum chemical calculations. Unsubstituted meso positions are essential for successful polymerisation, as demonstrated by varying the porphyrin meso substituent pattern from di‐ to tri‐ and tetraphenyl substitution. DFT calculations support the proposed radical oxidative coupling mechanism and explain the regioselectivity of the C−C coupling processes. Depositing the conjugated polymer on glass slides and on thermoplastic transparent polyethylene naphthalate demonstrated the suitability of the porphyrin material for flexible optoelectronic devices.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2019-05-01 | Chemistry – A European Journal |